Epoxy containing resins



' containing largely unaifectedt;

1 1 3,132,121 EPOXY lC NTAHQINGRESINS Ivan Pascal, Wilmington, Del, assignor to E. I. du Pont de Nemours and} Companyfllilmington, Del., 2 corporationof Delaware- 1 d No Drawing. Filed Apr. 13,1961, Ser. No. 102,672 1 T I 6 Claims. (Cl. 260-805) f This invention is directed to new polymeric materials containingepoxy groups. More particularly, the present invention relates to copolymers or interpolymers of fluoroolefins with alkyl vinyl ethersgand certain unsaturated 'epoxides. The copolymers comprise units of different monomers taken from each ofthe three respective different, groups of unsaturated compounds. The novel copolymers of -this invention are vulcanizable thermoplas- "tic materialshaving a tenacious adhesion to the surface of I a large variety of materials including-natural and synthetic rubbers, fluorine-containingresins, silicone resins,

resistance and toughness. These properties Well adapt the copolymers' for such uses as casting, -potting,;en-

' capsulating, sealing, coating, bindinggimpregnating and ilaini-nating.

@An existingfprobleinhas been to find a more univer v sally applicable vulcanizable or thermosetting composition than I he compositions now 1 available "to provide lsti 'ong ly adherent coatings to a large number of diifer ent materials, particularly to flourine-containing resins. 1

j A To mention one specific need, for example, there is required a pottingcompound ha ing -high adhesion both before' and after vulcanized .to the many different surfaces'which may be encountered in electrical equip,-

' ear'bon and sw eti resinsito which 1111s difiicult to make things s'tickQas; Well as to metal ian d 1111 11 1 the same i It is, therefore, an object 111-11111 invention to provide novel polymeric materials containing ,e'poxy groups: which cani be crlosslinked through the-opening of the poxy groups. 111% a further object toprovidepourable thermoplastic resins vvhich' are vulcanizztble to "tough" resilient solids andf-adlierent to the surface of mahy different maeluding resins;Pl Stic, -rubbers, metals-glass,

terials It 1511' fur her' object of thisinvention to provide epoxy 1 "These 'and othenobjects-vvillbecomecapparent in the v(following, descrip tion.and claimsglh V 1 TMore specifically; the presentiinve'nt'ion' 'isldirected 1'11 an epogry containing copolymer of (a) a po lymerizable .eriza'ble compounds of each 'grohp. a

eXamplq can be use 1 can be used'in'combination- 11111131111: epoxy-cont 3,132,121 Patented May 5,1964

stituted ethylene cont-ainingat least one fluorine atom and having the formula: 1 F' X wherein X is hydrogen, fluorine, chlorine, or trifluoromethyl and Y is H or F, and1,(c) an alkyl vinyl ether 'whereinjthe ally group is'C to C 'straight or branched chain. I v In said copolyrner, for each mole of component (b) there may be from 0.01 mole to 2 moles of component i (c) and from 0.01 mole .to 1 mole of component (a).'

,and subjecting theresulting composition to conditions under which cross-linkingoccurs.

The epoxy monomers utilized according to the prment invention are illustrated by suchcompounds as vinyl glycidyl ether, allyl glycidyl ether, glycidyl ,acrylate, glycidyl methaerylate, and 1,2-epoxy-4-vinyl cyclohexane;

The preferred epoxy monomer for the preparation of polymers for use as pottinglcompounds is allyl glycidyl ether. I 1 a J l Polymerizable -fiuoroolefins which can be used the preparation of the copolymers ofthis invention include: .Vinyl fluoride 1 d The preferred fiiioroolefinis tetrafluoroethylene. The alkyl vinyl'ethersWhichgnay be used in the practice of this invention include:

. Methyl vinyl ether ,Ethyl vinyl ether Prop'yl vinyl ether 1 1 Isopropyl vinyl ether 1 w-Butyl vinyl'ether ,Isobutyl'vinyl ether 1 Hexyl vinyl ether U That islia mixture -01 -allyl glycid'yl ether and gl'ycidylj inethacrylateajfor m Qrimiixflylll l p xy-containing monomers and anialkylj vinyl ether. Similarly,miXed alkyl vinyl "eth is can :be len ployed to produce the "novelproducts' of ginventionp 1 I g d V The desire'drelative proportions ofthe rnonorfiers are 1 polymerized the presence of a-chain-transfragent, optionallygan'aeid accepton and apolymerization 11111111: I

A d d well as' eithenepoxycontaining' compoundzin combinationwith'a fiuoroolefin and an alkyl vinyl ether-.3 Also, mix-tures of iiuorool'efinsj suchase "sion polymerization are run,

g'ro wing' olymer chain, generating in this process mono tor in bulk, i.e. without an added diluent, in solution, or Y in an aqueous emulsion. Preferably the polymerization reaction is carried out in an unpolymerizable organic solvent which may or may not be a solvent for the polymer. A reactor made of or lined with silver, stainless steel, monel metal, or. the like and capable of holding several hundred atmospheres of pressure is employed. Batch or continuous processes, when solution and emulare used to produce these copolymers."

'The use of a solvent as a reaction medium for the production of the copolymers of this invention facilitates handling of'the reactants and the products. in a continuous polymerization'process, the solvent can act as a convenient carrier of the liquid monomers, chain transfer agent, and polymerization initiator and provide Particularly,

a means of readycontrol of the relative concentrations 3 of these materials. Solutions of'the products are often easier to handle than viscous liquid or semi-solid prod- 'ucts. The solventfor the monomer, however, does not have to be a solvent for the polymer; the insoluble polymer may be dispersed in the solvent and handled as a slurry. A solvent canalso act as a heat exchange medium to dissipate the heat of polymerization. In addition, a solvent can function ,as a reactant of the chain transfer or telogen type and thus help control the molecular weight or the viscosity of the polymeric product.

Suitable solvents which may be utilized in the practice of this invention include nonpolymerizable aliphatic or alicyclic hydrocarbons, halocarbons, halohydrocarbons, alcohols, and ketones. To facilitate the removal and recovery of the solvent from the solution of the polymeric product, the solvent should have a boiling point of 150 C. .or less at 760 mm. pressure, and preferably of 100 C. or less. Compounds which can be used as liquid reaction media include hexane, heptane, octane, methylcyclohexane, carbon tetrachloride, 'tetrachloroethylene, 1,1;1-trichlorotrifluoroethane, 1,1,2- trichlorotrifluoroethane, -fiuorotrichloromethane, 1,2-difluorotetrachloroethane,'f 7 1,3 -bis(trifluoromethyl)perfluorocyclobutane, methanol, ethanol, l-propanol, 2-propanol, l-butanol, "2-butanol, 2-methyl-2-propanol, acetone, Z-butanone. It will he usually preferred to employ heptane or one or both of the isomeric trichlorotrifluoroethanes. Mixtures of any two or more of such solvents named herein may be used, if desired.

I barium oxide, calcium oxide,

cyclohexane,

chloroform,

The choice of a solvent will depend upon the amount of solvent reaction in the copolymerization that is desired; solvents which have relatively high reactivity and act as relatively strong telogens or chain transfer agents will lead to low molecular weight products. The amount,

uct of the invention while the dilutionobtained with more I than 20 parts of solvent becomes excessive. The pre- "ferred amount of solvent is 0.5 part to Ziparts per part 'of total monomers. The copolym'erization, may, of course, be carriedout in theabsenceof any'solvent;

A 'chain transf ragient isonewhich can terminate a an. other free radical' which can start another chain. 'used to obtain low molecularweight polymers which may be :fluidsl'or low melting' solids. A chain-transfer agent canbe the solvent, a cornpound added in r ers in a solventor boththe solvent andan, added 'Lagent, sometimes the only distinction-between the solvent and the chainatransfer agent isthat the .[solvent is em- It is elatively small "from about 0.2%

- loyed in a relatively larger amount to act both as 'a -re- .actant and as ,a reaction medium. table chain-transfer agents Compounds which are sui or use. in the copolymerization"according to the pres.-

and upon the molecularweight or viscosity particularly with benzoyl peroxide as cut invention are those, in general, which have an active hydrogen atom. This group includes such compounds as isobutane, methylcyclohexane, l-dodecanethiol, ethyl ether, isopropyl ether, cyclohexyl ether, tetrahydrofuran, 2-propanol, and the like. Preferably, volatile chain-transfer agents having a boiling point of C. or less are employed to simplify the removal of unreacted material from the reaction products. The chaintransfer agent can be used in an amount from about 0.1% based on the total monomers present, to such high concentrations that the agent may also be considered a solvent. The actual amount which will be used will depend upon the reactivity of the particular agent selected of the polymeric product which is desired.

When the highest molecular weight thermoplastic polymers are desired, the chain-transfer agent is eliminated and the solvent, if one is used, is relatively inert.

The acid acceptor which can be utilized in the practice of this invention is an anhydrous metal carbonate or oxide which neutralizes minor amounts of hydrofluoric acid that may appear in the polymerizing mixture. The acid can be an impurity in the starting fiuoroolefin monomer component of the system or it can be a by-product of the polymerization; its origin is not always known, but its presence tends to destroy epoxy groups, and products which have a lower epoxy content and are consequently slower to crosslink are obtained. Acid scavenging agents which can be used are the anhydrous form of such compounds as potassium carbonate, sodium carbonate, calcium carbonate, magnesium carbonate, aluminum oxide,

' magnesium oxide. The amount of the acid scavenger will vary from about 0.1% to about 10% by weight of the total monomers taken for polymerization, a preferred amount being 1% to 5%.

It will be understood that, while the presence of an acid scavenger or acceptor helps preservethe epoxy group during the copolymerization, the polymerization reaction ,can be run in the absence ofsuch an agent and useful polymeric products will be obtained.

An organic free-radical generating polymerization initiator is required to' initiate the copolymerization among the fluoroolefin, alkyl vinyl ether, and epoxy compound and .to produce the polymeric products of this invention. Such initiators are well known and are conventionally employed as catalysts for the polymerizationof olefins. Suitable initiators for the copolymerization in bulk or solution are organic peroxides, which include alkyl peroxides suchas diethyl peroxide, tert-butyl hydroperoxide, di-tert-butyl peroxide, and the acyl peroxides such as acetyl peroxide,- heptafluorobutyryl peroxide, lauroyl peroxide, and benzoyl peroxide; and the organic azo initiators: such as 2,Zf-azodiisobutyronitrile, and 2,2'-azobiz- (2,4-dimethyl 4-methoxyvaleronitrile) The preferred initiators are theorganic peroxides, particularly the acyl peroxides. Benzoyl peroxide is most preferred because it is active at a desired temperature range, it is readily available commercially, is stable in storage, and is easily handled. v

Usually, thefamount of initiator employed will be to about-4% by weight based'on the total monomer mixture, preferably 1% to 2% by weight,

the initiator.

In'an emulsion copolymer ization, in addition to the above-mentioned organicfree radical generating initia tors, such inorganic initiators as sodium peroxide, barium m the momma, mixture Orr- :[Q a Solution of the P roxide, ammomum persulfateppotassium persulfate, and

-thelike can be used.

The copolymerlzation may be carried out at a temperature of from about, 25 C. to about 200 C., the

particular temperature employed being dependent priing compound, a copolymerwhich is a viscous fluidpour- I with'a variety of crosslinking agents to convert the fluid 45L i or thermoplastic compositions into resilient, tough, stable,-

assembly and may permit the deteetion offailurevisual A",significantpropertywhich makes thepresent novel 55 t t t .pact, chemical attackQoxidatiOn, and electrical currents.

stability of the initiator sothatitwill decompose and generate its free radicals at a reasonable rate and at which the. free radicalscanbe usefully employed in pro- 'moting the reaction; Below 25C. the reaction tends to become too slow to be practical. Above 200 C. there '5 is a tendency for the epoxy ring to open with not only a loss of epoxy groups but witha resultant undesirable premature insolubilizing and stiffening of the polymer .by crosslinking. The reaction can be carried out at a v C. by employing an initiator suchas heptafluorobutyryl peroxide. The reaction can be carried out at about 80 C. by employing such an initiator. as benzoyl peroxide. The reaction can be carried out at about 120 C.to about 150 C. by employing ditert-butyl peroxide as the initiator. It is preferred to 5 'employbenzoyl peroxide at a temperature of from about 70 C. to about 100 C. Highertemperatures tend to give lower molecular weight products. I

The pressure under which the polymerization is carried out can be the autogenous pressure of the gaseous monomers at the polymerization temperature or it can be a superimposed pressure of one. to 1500 atmospheres. The superimposed pressure can be produced by an extraneous inert gas, such as nitrogen or'carbon dioxide, as well as by the gaseous monomers.

The novel copolymers'of the present invention vary from viscous fluids to low and high melting plastic ma--- terials. The fluidity and melting, temperature of the prod-' ucts depends upon such factors as the nature and. proportion of the monomers selected forthe copolymeriza- ,tion, the type and amount of the chain-transfer agent: present, and the temperature of the polymerization. Co; polymers made with 'allyl glycidyl ether, forexample,

-- tend to be more fiuid orlower melting than the copolymers made with glycidyl methacrylate. The use of in creased relative amounts of allyl glycidyl'ether in the monomer mixture increases the fluidity ofthe copolymer. The eifect ofthe type and amount of the chain-transfer agentand ofthe temperature has'jalready been discussed. Forgeneral use as a p-otting-,-encapsulating, and seal- 40- able at room temperature is preferredto a-plastic product which must be heated to render it fluid; The epoxy-con- I I taining copolymers of this invention can be compounded vulcanizates; .With' propercompounding, such as with a mixture of monoand dibutyl phospohates or of mono,- land diisooctyl phosphates as/cr osslinking agents, transparent vulcanizates are obtained: Such vuicanizates are. particularly useful in'the' electronic field'ibecause they rendervisible the conditionof the'component parts ofan inspection.

'copolymers particularly useful is its wetting of and ca pability; of strongadhesion'to practicall'yall surfaces; in- [eluding those ofpolytetrafluoroethylene, tetrafiuoroethyl ene copolymers; and silicone resins commonly. used for electrical insulationand which are, however, strongly anti,- 60. a it w s a a s.jiheiugtfina ji present novel copolymers of theseres-insas well as of Pl c rubbersaslassfind msta siwhiq imay so e present" in an electrical assembly-provides thoroughadhe-v sion. to all'parts of anassemblyj byIh iS 1YL PPl 1 potting, encapsula ing; or, sealing compound and leads to t e a u at in o the; sr ss nks ir tti "the surfaces with which it comes-into contact." LOtherpropert-ies of the crosslinketlfcopolymers ofithis invention which make; them significantly valuableflare their good-electric insulationpropertisicSiS aucc tu'cuttingand chipping, and"resistance--to-heat,-oils, solvents, aridchemiCals. .The "compounding and curing of the move copolymers Of hisi t on. a co nlis cd b we lr bwn p 7 amine, :m-phenylenediamine,

benzyldimethylamine, piperidine, oxalicacid,'maleic anhydride, phthalic anhydride, 50:50 mixture of monoand which'follows. 'T

dures for the compounding and curing of epoxy resins as is a compound which contains an acidic or basic group."

capable of reacting with the epoxy group of the resin. A bifunetional curing agent provides crosslinks between copolymer chains at the epoxy sites, and a monofunctional curing agent opens the epoxy ring to permit reaction with a second epoxy grou and provides a crosslink. Curing agents include aliphaticand aromatic amines and diamines, cyclic aliphatic amines, dibasic organic acids, acid anhydrides, mono and dialkyl phosphates. Specific representative crosslinking agents are ethylenediamine, diethylenetriamine, 1,4 butanediamine, 1,6 hexanedi- 4,4 methylenedianiline,

dibutyl phosphate. In addition to the curing agent, an epoxy resin may be compounded with fillers such as clays,

Whiting-carbonblacl; and the like, plasticizers, coloring pigments, etc.

Theheretofore-described compounded epoxy resins can be applied in pottin encapsulating, sealing, and coating.

by such meansas pouring, brushing, troweling, extruding from a gun. Hand guns are convenient, for example, for

potting connectors, coating strain gages, 'etc. Spray equipment may alsobe used to apply the compounded --resin.- a ff The jcrosslinking' of the compounded resin is accomplished from room. temperature to 200 'jothe'r than at the ambient temperature,

C. For curing ovens, infrared lamps and high frequency heaters can be used. Curing f can also be done withfthe aid of ultrasonic vibrations, and

electron and electromagnetic radiation. In general the {degreej'and rate of crosslinking under a given set of conditionsdepends upon the epoxy content of the resin and the'amouht and actiyity of the curing agent.

Mention has been made herein of such uses of the resenthov r copolymers, 'as for potting, i.e., the deep embedment and thorough impregnation of articles and assemblies of equipment; encapsulating, i.e., the surrounding or capsulatingan item with shielding material; sealing,i.e., cio .ing ,Oif portion of a device against the. environment;- coating of surfaces; binding in the preparatioii' 'of laminates'ofpaper, cloth, fiber glass,.wood sheets and the'like; "and for versatile adhesion. In each of these uses. the resin provides insulation against moisture, im-

Representative examples illustrating-the present exam 'ple follow."

I @Eidll P -97 Af400 ml. stainlesssteel shaker tube was charged with an :unsaturated epoxide, an alkyl vinyl ether, solvent,

chairr transfer. agentg jacid acceptor, and polymerization initiator. of -the..nature' and amount given in Table I he tube was then closed, cooled in a solidfcarbon dioxideracetone bath, evacuated, and filled with-pure nitrogen. While still cold the tubewas placed ongth e shaker'afid charged by condensation with thej,de-

siretlfquantity 'oftluoroolefin. The tube and its contents were heated electric y to the desired temperature while under agitation;

thep'olymeri'zation allowed to a ceed for from about 4 1 r mixture was cooled lo room temperature, removed from 1 7 .the -tube, 1 and allowe tofstand'. at room temperature to then filtered to remove the acid acceptor, and thesolvent, number is the fractional molecular equivalent of epoxide chain-transter agent, and any unreacted monomers were contained in 100 grams or" the copolymer. 7 "removed by evaportaion under vacuum. The polymeric 'The ingredients with the amounts used in a series of "residue was weighed and characterized by elemental polymerizations together with theweight and results of analysis and epoxide number determination. Theepoxide T5 analysis of the end products are presented in Table I.

Table 1 Example (a) Unsaturated epoxide G. Mole (b) Fluoroolefin G. Mole 57 0. 5 Tetrafluoroethylene 50 0. 5 28.5 0.25 50 0.5 28.5 0.25 50 0.5 38 0.33 50 0.5 5.7 0.05 50 0.5 11.4. 0.1 50 0.5 28 0.25 50 0.5 57 0.5 50 0.5 5.7 0.05 50 0.5 28.5 0.25 50 0.5 11.4 0.1 50 0.5 57 0.5 0.55

0. 11.4 0.1 y; igs

9 0. 24 0.375 28.5 58 0.5 5.88 0.5 0.58 0.5 28.4 0.5 14.2 0.5 14.2 0.5 14.2 0.5 14.2 0.5 7.1 0.5 71 0.5 do 14.2 0.5 1,2-epoxy-4-vinyl cyclohexane--. 31 0.5 Example (0) Alkyl vinyl ether G. v Mole Solvent M1. Chain-transfer M1.

' agent 72 1.0 Heptane 95 Tetrahydroiuram. 72 1.0 d 72 1.0 60 0. 83 72' I 1.0 72 1.0, 72 1.0 .72 1.0 72 v 1.0 72 1.0 72 1.0 72 1.0 72 1.0 72 1.0 72 1.0 do

3. 6 0. 05 1,1,2-triehloro tnfluoroethane. A 0.005. do

I V Temperature Weight of Initiator 1 G. oipolymericopolymer f zation, C. in g. 1

.Benzoyl peroxideim d0 Di-t-butylperoxide. J v g Benoylperoxide" 0-...'

Table I-Continued Analysis of copolymer Epoxide Example N o. of Physical state of copolymer Viscosity of copolymer copolymer Percent C Percent H Percent F 48. 9 5. 9 27. 5 0. 290 Viscous fluid 4,500 cps. 47. 3 5.8 34. 0. 152 do 1oo,o0o cps. 47. 0 5. 7 32. 9 0. 13 47. 5. 7 33. 7 0. 110 48. 9 5. 1 39.5 0.018 45. 4 5. 3 36. 1 0. 048 46. 4 5. 7 33. 8 0. 119 48.1 5. 7 32.2 0.211 d0 m= 0.1. 44. 0 5.1 41. 2 0.0165 -=0.13.

. 45. 6 5. 3 38. 7 0.117 d 20. 43. 8 5. 4 37. 9 0.045 d .16. 47. 6 6. 4 31. 8 0.20 do m=0.03. 50. l 6.0 27. 6 0. 040 47. 2 5. 8 34.6 0.06 do 44.1 5. 3 24. 0 0.109 do 1 i=0.1. 31. 2 2. 1 57. 4 Tough wax-like solid 24. 9 O. 3 72. 6 Brittle wax-llke solid 46. 2 5. 4 33. 7 0. 113 Viscous fluid 1 ;=0.187. 45. s 5. 4 3c. 7 o. 068 45. 1 5. 9 38. 3 0.076 m=0.20. 51. 5 6. 5 30. 1 0. 086 1,;=0.39 50. 9 6. 5 26. 7 0.080 m=0.25.

( Tough, white plastic solid 49. 4 5. 8 35. 0 0. 119 Viscous fluid 1 Measured with Brookfield viscometer at C. 2 No data.

3 Inherent viscosity, 1% solution in tetrahydrofuran.

. EXAMPLE 27 30 spirit and scope thereof, it Is to be understood that this COMPOUNDING AND CURING 0F COPOLYMER invention is not llmrted to the specific embodlments there- 7 of except as defined in the appended claims.

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as With 10 parts .of the fluid copolymer of Example 2 were mixed 1.15 parts of an equimolar mixture of monoisooctyl and diisooctyl acid ortho-phosphate with stirfoHows ring. The resultant composition was poured into a mold 1 1 6 poxy contalning copolymer consisting essenig fi g i 3 at temperature tially of (a) a polymerizable ethylenically unsaturated urmg 18 6 qngma copo ymer was q epoxide free from aromatic unsaturation and having the lmked to flexlble hlgialy reslhent. translucent epoxide group non-adjacent to the double bond, (b) at W the abpve moldmg and curing was repeaied wlth 40 least one substituted ethylene having the formula strlps of aluminum, copper, and steel metal, pieces of polytetrafluoroethylene resin coated wire, sections of gig glass rod, pieces of porcelain, rods of formaldehyde- Y X Phen01 type of Plastic Plates of Poly methyl methacry' wherein X is selected from the group consisting of hydrolate f Ships of imbedded in the composition gen, fluorine, chlorine, and trifiuoromethyl, Y is selected the flu d polymer readily wet the surfaces of these driferfrom the group consisting of H and F, and (c) an alkyl ant After, the copolymer sohdlfied on standmg vinyl ether wherein the alkyl group is a C to C straight the crosshnked resin adhered fimlly to metals and a C to C branched saturated hydrocarbon radical; tetrafluoroethylene, glass, porcelain, plastlcs, and nylon. and wherein for each' mole of said substituted ethylene EXAMPLE 28 there is 1igireseng irom mole to 12 niolesdof saiddalkyl viny et er an rom to mo e o sai epoxi e. g gz gz ig g g gg g f gy gsg figfi 5 2. A copolymer of claim 1 wherein the component (a) d l S-terminal solid shell straight aluminum cable connector ii i g glycldyl ether an 9 (c) 1s ethy Y plug i alpspiwe W the terminals connected 3. A copolymer of claim 1 wherein the component to the wires andslmatedpslde t h shell of the 9 (a) is allyl glycidyl ether, component (b) is tetrafluoronector plug, Was filled w th the llqllld polymer descnbed ethylene and component (c) is ethyl vinyl ether and comp9unded as Example 4. A copolymer of claim 1 wherein component (0) is After standing at room temperature for 24 hours, the methyl vinyl ethen initially liquid l a x hlghly 5. A copolymer of claim 1 wherein component (a) is rent, translucent material providing a tlght seal around vinyl glycidyl ethen the wires leading to the terminals of the cable connector 6. The vulcanized product obtained by mixing a polymer according to claim 1 with a vulcanizing agent Is understood that the precedmg exampieis may.be followed by vulcanizing the resulting composition. varied, both as to reactants and reaction conditions, within the scope of the present total specification as under- References Cited in the file patent stood by one skilled in. the art to achieve essentially the r same results UNITED STATES PATENTS As many apparently widely difierent embodiments of 2,626,252 Tawney Jan. 20, 1953 this invention may be made without departing from the 2,692,876 Cupery Oct. 26, 1954 

1. AN EPOXY CONTAINING COPOLYMER CONSISTING ESSENTIALLY OF (A) A POLYMERIZABLE ETHYLENICALLY UNSATURATED EPOXIDE FREE FROM AROMATIC UNSATURATION AND HAVING THE EPOXIDE GROUP NON-ADJACENT TO THE DOUBLE BOND, (B) AT LEAST ONE SUBSTITUTED ETHYLENE HAVING THE FORMULA 